N- and n{40 -substituted n-bromoacetyl ureas

ABSTRACT

The specification discloses a group of N- and N&#39;&#39;-substituted Nbromoacetyl ureas which have been found useful in the treatment of soil and seed, because they have a broad biocidal activity.

United States Patent [72] Inventors Ludwig Nussleln;

Ernst Albrecht Pieroh, both of Berlin, Germany [21] Appl. No. 746,710[22] Filed July 18, 1968 [45] Patented Dec. 14, 1971 [73] AssigneeSchering AG Berlin and Bergkamen, Germany [32] Priority Sept. 19, 1967[33] Germany [31] P 16 43 039.0

[54] IN- AND N'-SUBST1TUTED N-BROMOACETYL UREAS 30 Claims, No Drawings[52] U.S. Cl 260/309.7, 260/347.3, 260/465.4, 260/482 R, 260/553 A,260/553 E, 424/273, 424/285, 424/304, 424/311, 424/ 3 22 .1 leiso 1Field 0! Search 2150/3091,

553 E, 553 A, 482 R, 465.4, 347.3

[56] References Cited UNITED STATES PATENTS 2,562,863 7/1951 Hoegberg260/553 2,801,200 7/1957 Hackmann 167/22 3,184,507 5/1965 Scherer et a1260/553 3,261,865 7/1966 Speziale et a1. 260/553 3,301,896 1/1967 Haymanet a1 260/553 OTHER REFERENCES Gut et aL, Collection Czechoslov. Chem.Communs. 24, 3,154- 3,162 (1958) original unavailable, therefore C.A.54:4,61 1 has been supplied] Primary ExaminerHenry R. Jiles AssistantExaminer-G. Thomas Todd Attorney-Joseph F. Padlon ABSTRACT: Thespecification discloses agroup of N- and N'- substituted N-bromoacetylureas which have been found useful in the treatment of soil and seed,because they have a broad biocidal activity.

N- AND N '-SUBSTITU'IED N-BROMOACEI'YL UREAS The invention relates tobromoacetyl ureas having biocidal action. More particularly, theinvention relates to bromoacetyl ureas for the treatment of soil andseeds.

ried out in the usual manner such as by grinding or mixing processes.

it is to be noted that the active substances have not heretofore beendescribed in the literature with possibly one excep- Heretofore, ureaderivatives have become known predomi- 5 tion, namely bromoacetyl urea,per se. The production of nantly only with herbicidal action. A broadbiocidal action has these compounds is affected for example by thefollowing not been observed in such compounds until now. methods, suchas: V my The compounds covered by the invention have a fungicidal, Wherecompounds O the general fo mula fungistatic, nematocidal and herbicidalaction, and therefore are suitable chiefly as soil and seed treatmentagents. 10 H R;

in the stated general formulaabove, the radicals R may have, thefollowing meaning: R represents hydrogen or an alkyl group, such asmethyl or ethyl, etc.; R, represents hydrogen, aralkyl, such as benzyl,etc., cycloalkyl with r w. preferably three to eight ring members, suchas cyclopropyl, wherein R, R, and R, having the above-mentioned meaning,cyclopentyl, cyclohexyl, cyclooctyl, etc., or possibly saturated arereacted with compounds of the general formula or unsaturated alkylmonoor multisubstituted by halogen, such as chlorine or bromine, etc.,and/or alkoxy, such as r- 4 methoxy or ethoxy, etc., and/or cyanogenand/or alkylmerwherein is halo en or the u BIC" or if in capto, such asmethylmercapto, andior carbalkoxy, such as the abovfgeneml g g fhyamgen; or v carbethfxy and/0' a mmmyqhc f h as alphamryl' b. wherecompounds of the general formula etc., which alkyl may bestraight-chained or branched and preferably contains up to six carbonatoms, such as methyl, ('J N R ethyl, to hexyl, isopropyl, secondarybutyl, tertiary butyl, allyl, among others; R, represents hydrogen,bromoacetyl or the with bmmmtamlde ofthe formulatrihalogenmethylmercapto methylmercapto radical, such as thetrichloromethylmercapto radical, among others; and R BKCH: CO NH' and R,represents together with the FN-CO-NE groups, at where the reactions arecarried out preferably in the presence least a five-memberedheterocyclic ring, such as that of N,N of inert organic solvents and, ifnecessary, with the addition of ethylene urea. 3 acid-binding substancesat temperatures in the range of about These compounds display inparticular an excellent funl5toabout 150 C. gicidal and fungistaticaction and can therefore be used for in- The reaction partners arecharged in approximately stance in agriculture or horticulture,particularly for general equimolecular quantity. soil treatment. Besidesthe control of soil-growing fungi, plant- Inert organic solvents,chlorinated organic hydrocarbons, parasitic nematodes and seed weeks,e.g., Senecio vulgaris, ethers, nitriles and amides have provedsatisfactory, such as Chenopodium album, Stellaria media, are alsoaffected. The chlorobenzene, dioxane, acetonitrile, acetic ester andcompounds are more or less suitable also as disinfectants for dimethylformamide may be used in the reactions. seedtreatmenttoparasitic fungion the seed. The reaction occurs at temperatures in the range from Withrespect to their fungicidal and fungistatic efficacy, the about 15 toabout [50 C. To accelerate the reaction and to active substances areeven'superior, surprisingly, to the best 40 bind the hydrogen halideforming when bromoacetyl halides known compounds of equal direction ofaction, as the comare used, there may be added tertiary amines, such asparative experiments cited below will show. triethylamine or pyridine.The reaction mixture may be The active substances may be used alone oras mixtures of processed by distilling the solvent and recrystallizingthe several active substances. If desired, other fungicides,nematoresidue in a suitable solvent. Another method is to precipitatecides, herbicides, disinfectants or other pest control agents thereaction product with water and to recrystallize it after can be added,depending on the desired purpose. For examseparation by filtration. ple,if a herbicidal use is intended, fertilizers may also be used Theresulting bromoacetyl ureas are free from byproducts in the mixtures.Advantageously, the active substances are and the yields are good. usedin the formof preparations, such as powders, dusts, The followingexamples illustrate the production of the acgranulates, solutions,emulsions or suspensions, with addition tive compounds. of liquid and/orsolid vehicles or diluents, and possibly with l. N-n-butyl-Nbromoacetylurea wetting, adhesion, emulsification and/or dispersion aids.Fifty-eight g. of n-butyl urea are dissolved in 200 ml. of

Suitable liquid vehicles that may be used in conjunction'dimethylformamide and 40 ml. of pyridine. Then, while coolwith he a tivec mpo n are water. mineral oils r other ing with water, 101 g. ofbromoacetyl bromide are added in g n solvents. such as xy h n n y x ndrops with continued stirring for 30 minutes, after which iced ycl h x nn i n ni ril acetic ester. dimethyl water is added to form theprecipitate. The suction-filtered formamid and imethyl ulf xi m ng hreaction product is recrystallized from 300 ml. of acetonitrile.

As solid vehicles that are suitable are lime, kaolin, chalk, Yield: 57g.#8 percent of the theory. talcum, attaclay and other clays as well asnatural or synthetic 2. N,N-bisbromoacetyl-ethylene urea silica. 60 21.5g. of ethylene urea are dissolved in ml. of dimethyl Amongsurface-active substances that may be named are formamide at 100 C. Tothis are added g. of bromoacetyl $8118 o g n sulfonic acid. salts ofalkylated benzenesulfonic' bromide, and the resultant mixture is cooledso that the temacids, sulfonated acid amides and their salts,polyethoxylated perature does not rise above 120 C. After a h lf-hamines and alcohols. tion, the conversion product is precipitated iniced water, suc- If the active substances are to be used for seeddisinfection, tion-filtered, and recrystallized from ethanol. Yield: 52g.=63 dyes such as New Fuchsine among Others, may be ix o percent of thetheory. give the disinfected seed material a clearly visible color. Inthe following table, additional active substances to be Theproduction ofthe various forrns of preparation is car: used invention arelisted. k A

Physical No. Name of compound constant, C.

1 N-brcmoacety1-N-methylurea .4 l 189 2 N-bromoacetyl-N-ethy1urea. 144 3N-bromoacetyl-N-propyl urea 134 4 N-bromoacetyl-N-isopropylurea. 84 5N-bromoacetyl-N-cyclopropy1 urea 126 of the powder preparations, therefollowed without a waiting 6 N-t romoalcetyl-N allyl urea 135) 7N-bromoacetyl-N-isobutyl urea.-. 140 N-bromoacetyl-N-tertiary butylurea. 110

9 N-bromoacety1N-n-amyl urea 128 N-brm0acety1N-n-hexyl urea 123N-bromoacetyl-N'-benzy1 urea. 172

N-bromoacety1-N-fu.rfury1 urea. 168

N-bromoacetyl-N N-ethy1ene urea 173 N-bromoacetyl-N-trichloromethylmercapto-N,N-ethylene urea. 118N-bromoacetyl-N-beta-ch1oroethyl urea t 141N-bromoacety1-N-beta-bromoethyl urea 136N-brornoacety1-N-beta-methoxyethyl urea 136 tN-brornoacetyl-N-beta-pheny1ethy1 urea 138N-bromoacetyl-N-gamma-methoxypropyl urea 100N-bromoaeetyl-N'-cyanomethy1 urea 146N-bromoaeetyl-N-gamma-n-butoxypropyl urea- 76N-bromoacetyl-N'-isopropoxypropylurea 60N-bromoaeetyl-N-beta-methylmercaptoethyl urea. l 137N-bromoacetyl-N-gamma-ch1oropropy1urea 111N-bromoacetyl-N-4-ch1orobutylurea 126N-bromoacetyl-N-4-methylmercaptobuty1 urea 1 97 27N-bromoacetyl-N-carbethoxymethy1urea 164 1 With decomp.

EXAMPLE 2 The smwd melting m the above column me not Steamed compostsoil was inoculated with a spore suspenrecwdsion of Fusarium oxysporum,F. callrstephl. After homogene- The w i P "Qcrymllim wbmnc one mixing ofthe products with the infected soil, the products "f characmnfmc meltingPoint P 50mm? m were present as 20 percent of the powder preparations,there chlorinated organic hydrocarbons, ethers, mtnles and amides,followed after a waiting i d f 5 days the planting of three such aschlorobenzene, dioxane, acetomtnle, acetic ester, and sewing of the hostplant wit-staph": Chinmsis Mas"er An dimemylfoflqwideu Sunray," perconcentration. In the table, there is given the The following exampleswill explain the biocidal action of number of affected plan an" acultivation period of 3 the compoundsweeks. As known comparativeproducts, there was used CAP- EXAMPLEI 11:11:)(N-(trichloromethylthio)cyclohex-4-ene-1,Z-carboxi- Steamed compost soilwas inoculated with mycelium of I 1 WM Pythium ultimum. Afterhomogeneous mixing of the products Copcentrat with the infected soil,the products were present as 20 percent gg gg Attack per liter afterperiod, per concentration, the sowing of 25 grains of marrow Pmducts on3 peas of the variety Miracle of Kelvedon" in clay dishes hold- 200 0ing 1 m ofsoiL N-bromoacety1-N-ethyl urea 28g 3 In the following tableare stated the number of germinated p 200 0 healthy peas and the rootrating (1-4) after a cultivation Nmmmmcetylurea 28g 8 period of 26 daysat 22 to 25 C. As known comparative I 200 0 products, there .were usedMANEB (manganese(II)-/N,N'-- Ntiromacetyl'N 'auylm'ea 288 gethylene-bis(dithiocarbamate and CAP'IAN (N I 200 3 (gighlqrgr retllthio)-cyclohex-4-ene-1,2-dicarboximide). N'bmmoacetyl'N'N 'ethyleneurea 283 ii Concentra- Number tion, mg. of healthy Root active subst.peas after rating Product used per 1t. soil 26 days (1-4) N-br0moacety1-N -ethy1 urea 83 Z V 20 4 N -bromoacetyl urea 20 4N-bromoacetyl-N-a11yl urea. 38 2 N-bromoacetyl-N,N-ethy1ene urea 38 $2 2N-bromoacetyl-N-n-propyl urea 3g i N-brom0acety1-N-beta-methoxyethylurea 88 2 -N-bromoacetyl-N-beta-ch1oroethyl urea S3 N-N-bis-bromoacetyl-ethylene urea 3g i N-bromoacetyl-N-cyc1o-propy1 urea 3gi N -bromoacety1-N -isobutyl urea 8g MANEB 123 2 1 CAP'IAN 88 g Steamedsoil (3 control tests):

Norm- ROM ratingz4=white roots without fungus necroses; 8=wh1te roots,slight fungus necroses; tbmwll roots, more advanced fungus necroses;1=advanced fungus necroses, roots rotte.

'. "iiiiitaieeaeaaanzaf mgiciaaraeabn at homogeneous B N -bromoacety1-Nbenzyi urea Q EXAMPLE 4 l 400 0f the products listed,N-bromoacetyl-N-furfuryl urea N bmmoacety1 N/ hexy1urea 3 shows a veryhigh plant tolerance. Tomatoes sprayed dripping 400 0 wet with aconcentration of 0.5 percent substance, for exam- N-bromoacetyl-N-isopropyl urea g p W no plan f 1 I 1 400 0 Asdisinfectant, approximately 1 g. of active substance per N'bmmoacetyurea 200 8 kg. of peas is sufficient for a good result, as the followingex- 200 g periment shows. N40mmoacetyLNLbetwmethoxvethfl urea" 300 0 oPeas disinfected with a 50 percent formulationwere sown in 400 0 normalcompost $011, grains of peas of the variety Miracle Nbmmoacety1 N, betachlomethy1urea 288 8 of Kelvedon (marrow pea) per concentration. After acul- 400 0 tivation time of l4 days of 22-25 C., the number of ger- NNLbi bromoa e[ I-ethylene urea g minated p was determined As comparative33g 8 products, there were used CAPTAN (N-(trichloro-methyl- Nbmmoacety1.Nlwclopmpyl um 300 0 5 h y h n .2- r mi NE (m nggg 8 ganese(ii)-/N,N'-ethylene-bis(dithiocarbarnate)/ and PM! D N-bromoacet,yl-N-furfuryl urea 300 0 (Tetramethyl'thwmm'dlsulfide)' $88 3CAPTAN 300 3 Number of healthy 400 3 20 peas, active substance teamedsoil: 0 per kg.

A 0 Product 0.5 g. 1.0 g. 2.0 g.

Steamed soil, seed Without disinfection (2 Xenia-o1 tests):BI::IIIIIIIIIIII1:111:11: EXAMPLE 3 Untreated soil, seed withoutdisinfection (2 control tests): A

mixing of the products with the infected soil are given below..Assumption in the evaluation are sound root formation and a germinationof the seed of at least 90 percent as against the achieved result in thesteamed soil. Per concentration, there occurred the sowing of 25 grainsof peas of the variety "Mira- EXAMPLE 5 cle of Kelvedon (Marrow pea)without waiting period. The K the following product! an admixed at a mmof 200400 cultivation period in the ex riments was 21-26 days at a tem-'perature of 22-25 C. As c omparative products, there were ofacuvesubstance of to a highly Infected by root gell nematodes (meioidogyns)and cucumbers are used MANEB (Manganese (ll)-/N,N-ethylene-bis(ditlnocar- 40 bamate)/ and CAP'FAN(N-(tri'chloromethylthimcyclohexsowed after a waning penod of 8 days thecucumber zdicarboximide) seedlings remain without visible root gallattack after a cultivation period of 4 weeks at 2245 C.

N-bromoacetyl urea (a) Pythium ultirnum: Steamed compost soil wasinoculated with mycelium of N'bTOmOacetYI'NI'methYI urea Pythiumultimum. N-bromoacetyl-N-ethyl urea (b) So-called dampingolf For thisexperiment, normal 7 N b l N l l urea compost soil was used. (c)Rhizoctonia solani: Steamed compost soil was N-bionjoacetyl-N n'amyl uminoculated with mycelium of N,N -b1sbromoacetyl-ethylene urea Rhizome!wllni- N-bromoacetyl-N'-beta-chloroethyl urea LIMIT CONCENTRATIONS OFFUNGICIDAL EFFECT lMg. of active substance per liter of soil] 1 Rhizoc-Pythium Dampingtonia Product ultimum ofi fungi solzmi N-bromoacetylurea. 26-50 -200 CAPTANIIIIII:IIIIIIIIIIIIIIIII N-bromoacety1-N-methylurea N-bromoacety1-N-ethyl urea. N-brornoacetyl-N-n-propyl urea sN-bromoacety1-N-isopropy1 urea fiiifififiii ti'fi '1 1 1a -8 y 6 N-bromoacetyl-N-n-butyl urea. N -bromoacetyl-N -isobut'yi urea. N-bromoacetyl-N -tert.butyl urea N -b1'0m0acety1-N -hexy1 urea N-bromoacetyl-N-n-amyl urea N-bromoacetyl-N'-benzy1 ureaN-bromoacetyl-N-iurfury1ure N -bromo'acetyl-N -N -ethylene urN,N-bisbromoacety1ethylene urea. N-bron10acety1-N-betachloroethyl urea.N -bromoacety1-N -betamethyoxyethyl u: N-br0moacetyi-N-betabromethylurea. N-bromoacetyl-N:-betaphenylethyl urea. N -bromoacetyI-Nmethoxypropyl urea- N-bromoacety]-N -cyanomethyl urea N-hromoacetyi-Ngamma-n-butoxy-propyi urea. N-bromoacetyi-N-isopropoxy-propyl urea-N-bromoacetyl-N-beta-methyi-mercaptoethyl urea N-bromoacetyi-N-ge.mma-chloro-propyi urea fimacetyLN-4-chlorobutyi ureaEXAMPLE 6 Field Experiment A soil highly infected by Fusarium oxysporumF callirrephi was treated with the products at the stated rates byhoeing to a depth of 10-15 cm. After a waiting period of two weeks,there occurred, per concentration, the planting of 20 ester seedlings ofthe delicate Master Aster Sunray." The table gives the plant loss aftera cultivation period of weeks, in percent. At the same time, theherbicidal action was determined by counting the germinated weeds.

Plant loss wherein R when taken alone is hydrogen; R, when taken aloneis selected from the group consisting of alkylphenyl wherein the alkylgroup contains from one to two carbons, furfuryl, cyclopropyl, alkyl offrom one to six carbons, alkenyl of three to six carbons, alkoxyalkylwherein the alkyl group contains from two to carbons and alkoxy containsfrom one to four carbons, chloroand bromoalkyl of from one to sixcarbons, cyanoalkyl of from one to six carbons, methylmercaptoalkyl offrom one to three carbons, trichloromethylenemercapto, andcarbethoxymethyl; and when taken together R and R is ethylene.

2. The compound as set forth in claim 1 comprising N-bromacetyl-N'-methyl urea.

3. The compound as set forth in claim 1 comprising N-bromoacetyl-N'-ethyl urea.

4. The compound as set forth in claim 1 comprising N-bromoacetyl-N'-propyl urea.

5. The compound as set forth in claim 1 comprising N-bromoacetyl-N-isopropyl urea.

6. The compound asset forth in claim bromoacetyl-N'-butyl urea.

7. The compound as set forth in claim ,bromoacetyi-N'-cyclopropyl urea.

8. The compound as set forth in claim bromoacetyl-N-allyl urea.

9. The compound as set forth in claim bromoacetyl-N'-isobutyl urea.

10. The compound as set forth in claim 1 comprising N-bromoacetyl-N'-tertiary butyl urea.

11. The compound as set forth in claim bromoacetyl-N'-n-amyl urea.

12. The compound as set forth in claim 1 comprising N-bromoacetyl-N-n-hexyl urea.

13. The compound as set forth in claim bromoacetyl-N'-benzyl urea.

M. The compound as set forth in claim bromoacetyl-N-furfuryl urea.

15. The compound as set forth in claim bromoacetyl-N,N'-ethylcne urea.

16. The compound as set forth in claim 1 comprising N-bromoacetyl-N'-trichloromethylmercapto-N,N-ethylene urea.

17. The compound as set forth in claim 1 comprising N- bromoacetyl-Nbeta-chloroethyl urea.

18. The compound as set forth in claim 1 comprising N-bromoacetyl-N'-beta-bromoethyl urea.

19. The compound as set forth in claim 1 comprising N- bromoacetyl-N'-beta-methogryethyl urea.

20. The compound as set forth in claim 1 comprising N,N'-his-bromoacetyl-ethylene urea.

21. The compound as set forth in claim 1 comprising N-bromoacetyl-N'-beta-phenylethyl urea.

. 22. The compound as set forth in claim 1 comprising N-bromoacetyl-N-gamma-methoxypropyl urea.

23. The compound as set forth in claim 1 comprising N- bromoacetyl-N'-cyanomethyl urea.

24. The compound as set forth in claim 1 comprising N-bromoacetyl-N-gamma-n-butoxypropyl urea.

25. The compound as set forth in claim 1 comprising N-bromoacetyl-n-isopropoxypropyl urea.

26. The compound as set forth in claim 1 comprising N-bromoacetyl-N-beta-methylmercaptoethyl urea.

27. The compound as set forth in claim 1 comprising N-bromoacetyl-N'-gamma-chloropropyl urea.

28. The compound as set forth in claim 1 comprising N-bromoacetyl-N'-4-chlorobutyl urea.

29. The compound as set forth in claim 1 comprising N-btomoacetyl-N-4-methylmercaptobutyl urea.

30. The compound as set forth in claim 1 comprising N-bromoacetyl-N-carbethoxymethyl urea.

l I i 1 comprising N- 1 comprising N- 1 comprising N- 1 comprising N- 1comprising N- 1 comprising N- 1 comprising N- 1 comprising N-

2. The compound as set forth in claim 1 comprisingN-bromacetyl-N''-methyl urea.
 3. The compound as set forth in claim 1comprising N-bromoacetyl-N''-ethyl urea.
 4. The compound as set forth inclaim 1 comprising N-bromoacetyl-N''-propyl urea.
 5. The compound as setforth in claim 1 comprising N-bromoacetyl-N''-isopropyl urea.
 6. Thecompound as set forth in claim 1 comprising N-bromoacetyl-N''-butylurea.
 7. The compound as set forth in claim 1 comprisingN-bromoacetyl-N''-cyclopropyl urea.
 8. The compound as set forth inclaim 1 comprising N-bromoacetyl-N''-allyl urea.
 9. The compound as setforth in claim 1 comprising N-bromoacetyl-N''-isobutyl urea.
 10. Thecompound as set forth in claim 1 comprising N-bromoacetyl-N''-tertiarybutyl urea.
 11. The compound as set forth in claim 1 comprisingN-bromoacetyl-N''-n-amyl urea.
 12. The compound as set forth in claim 1comprising N-bromoacetyl-N''-n-hexyl urea.
 13. The compound as set forthin claim 1 comprising N-bromoacetyl-N'' -benzyl urea.
 14. The compoundas set forth in claim 1 comprising N-bromoacetyl-N''-furfuryl urea. 15.The compound as set forth in claim 1 comprisingN-bromoacetyl-N,N''-ethylene urea.
 16. The compound as set forth inclaim 1 comprisingN-bromoaCetyl-N''-trichloromethylmercapto-N,N''-ethylene urea.
 17. Thecompound as set forth in claim 1 comprisingN-bromoacetyl-N''-beta-chloroethyl urea.
 18. The compound as set forthin claim 1 comprising N-bromoacetyl-N''-beta-bromoethyl urea.
 19. Thecompound as set forth in claim 1 comprisingN-bromoacetyl-N''-beta-methoxyethyl urea.
 20. The compound as set forthin claim 1 comprising N,N''-bis-bromoacetyl-ethylene urea.
 21. Thecompound as set forth in claim 1 comprisingN-bromoacetyl-N''-beta-phenylethyl urea.
 22. The compound as set forthin claim 1 comprising N-bromoacetyl-N''-gamma-methoxypropyl urea. 23.The compound as set forth in claim 1 comprisingN-bromoacetyl-N''-cyanomethyl urea.
 24. The compound as set forth inclaim 1 comprising N-bromoacetyl-N''-gamma-n-butoxypropyl urea.
 25. Thecompound as set forth in claim 1 comprisingN-bromoacetyl-N''-isopropoxypropyl urea.
 26. The compound as set forthin claim 1 comprising N-bromoacetyl-N''-beta-methylmercaptoethyl urea.27. The compound as set forth in claim 1 comprisingN-bromoacetyl-N''-gamma-chloropropyl urea.
 28. The compound as set forthin claim 1 comprising N-bromoacetyl-N''-4-chlorobutyl urea.
 29. Thecompound as set forth in claim 1 comprisingN-bromoacetyl-N''-4-methylmercaptobutyl urea.
 30. The compound as setforth in claim 1 comprising N-bromoacetyl-N''-carbethoxymethyl urea.